US4528333A - Curable, iminated resins from aminoplasts and hydroxyl-containing carboxylic acids - Google Patents

Curable, iminated resins from aminoplasts and hydroxyl-containing carboxylic acids Download PDF

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US4528333A
US4528333A US06/594,185 US59418584A US4528333A US 4528333 A US4528333 A US 4528333A US 59418584 A US59418584 A US 59418584A US 4528333 A US4528333 A US 4528333A
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resin
acid
hydroxyl
ungelled
resins
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Wen-Hsuan Chang
Robert Piccirilli
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PPG Industries Inc
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PPG Industries Inc
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Assigned to PPG INDUSTRIES, INC., A CORP OF PA. reassignment PPG INDUSTRIES, INC., A CORP OF PA. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: PICCIRILLI, ROBERT, CHANG, WEN-HSUAN
Priority to CA000476757A priority patent/CA1242839A/en
Priority to DE8585103472T priority patent/DE3563213D1/de
Priority to EP85103472A priority patent/EP0158874B1/en
Priority to ES541571A priority patent/ES8607360A1/es
Priority to JP60066426A priority patent/JPS60228524A/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/32—Modified amine-aldehyde condensates

Definitions

  • This invention is directed to an ungelled, curable thermosetting resin produced from an aminoplast, a hydroxyl-containing carboxylic acid, an alkylenimine, and optionally a polyol. More particularly, this invention is directed to such a thermosetting resin prepared from an alkylated melamine-aldehyde condensate, a hydroxyl-containing carboxylic acid, a low molecular weight diol, and an alkylenimine.
  • thermosetting reaction products produced by reacting an amine-aldehyde condensate, such as a melamine-formaldehyde or urea-formaldehyde resin with a polyfunctional material containing both hydroxyl and carboxyl groups. It is disclosed that these reaction products can include other components such as a polyol or an epoxy resin, diols being preferred as are epoxides such as reaction products of epichlorohydrin and Bisphenol-A.
  • the disclosed primary utility for the thermosetting reaction products of U.S. Pat. Nos. 3,965,058 and 3,502,557 is in water-dispersed compositions in which the vehicle comprises such reaction products alone or in combination with other resins which compositions are applied to a substrate by electrodeposition.
  • U.S. Pat. No. 3,519,627 to Coats is directed to cross-linking agents primarily for anionic electrodeposition compositions.
  • the cross-linking agents are produced by introducing carboxyl groups into amino-triazine/aldehyde condensates by transetherifying an alkoxy-alkyl amino-triazine with a mono- to di-hydroxy aliphatic carboxylic acid in the presence of an acid catalyst or by etherifying an alkylol amino-triazine with a mixture of aliphatic monoalcohol and a mono- or di-hydroxy aliphatic carboxylic acid in the presence of an acid catalyst.
  • U.S. Pat. No. 4,026,855 to Parekh et al is directed to a coating composition primarily for use in electrodeposition containing (A) an aqueous dispersion of a mixture of an ungelled modified cross-linking agent comprising an aminoplast cross-linking agent modified by reaction with a hydroxyl-group containing carboxylic acid, and (B) a water dispersible non-gelled polymeric material of certain description, and (C) an acid solubilizer.
  • thermosetting resins are good for certain coatings applications, they are deficient in a number of respects for use in coating formulations containing crosslinking agents based on aminoplast resins.
  • the present invention is directed to ungelled, thermosetting resins which not only can be used advantageously to replace at least a portion of aminoplast crosslinking agents, particularly melamine-aldehyde type condensates, in coating compositions, but also exhibit outstanding properties which make them exceptionally suitable for use as pigment dispersing resins (sometimes referred to as pigment grinding resins.)
  • the ungelled thermosetting resins of the present invention for example, can be used directly in place of known melamine-aldehyde crosslinking agents without the reduction of properties that can occur in both the uncured compositions and in cured films prepared therefrom when known acrylic or polyester pigment dispersing resins are employed.
  • An ungelled, thermosetting resin of the present invention when employed as a pigment dispersing resin, can function both as a crosslinking agent for other components of a coating composition and as a grinding resin without providing deleterious effects associated with the use of a number of known pigment dispersing resins.
  • the ungelled, thermosetting resins of the present invention can be used in a wide variety of coatings systems since so many coating compositions depend on an aminoplast, especially a melamine-aldehyde condensate, to effect curing.
  • thermosetting resins of the present invention can be employed in coating compositions for providing elastomeric, cured films having an excellent combination of hardness and flexibility.
  • thermosetting resins of the present invention when employed as pigment grinding resins, provide outstanding color development and excellent transparency in the grinds even for such hard-to-grind pigments as transparent red iron oxide. Resins of the present invention also tend to provide for excellent flow out of pigmented compositions containing conductive black pigments over various primers.
  • thermosetting resins of the present invention can be produced at very high solids (as will be defined infra), they can be employed in high-solids coatings applications without disadvantageously decreasing the total solids content of the coating compositions.
  • a resin of the present invention can be employed as the major film-forming component of a thermosetting coating composition, but is especially useful for various purposes as a modifying component of thermosetting compositions.
  • the present invention provides for an ungelled, synthetic thermosetting resin and a method of making an ungelled, synthetic resin which is a reaction product of components comprising: an aminoplast, a hydroxyl-containing carboxylic acid, and an alkylenimine.
  • a preferred resin of the invention is a reaction product produced from components comprising the aforesaid components in addition to a low molecular weight polyol, especially a low molecular weight diol.
  • the present invention also provides for a composition useful for coating a substrate comprising an ungelled, synthetic resin of the present invention.
  • Aminoplast resins are aldehyde condensation products of melamine, urea, and similar compounds; products obtained from the reaction of formaldehyde with melamine, urea or benzoguanamine are most common and are preferred herein.
  • condensation products of other amines and also amides can also be employed, for example, aldehyde condensates of triazines, diazines, triazoles, guanadines, guanamines and alkyl- and aryl-substituted derivatives of such compounds, including alkyl- and aryl-substituted ureas and alkyl- and aryl-substituted melamines.
  • Some examples of such compounds include methylurea, benzourea, dicyandiamide, formaguanamine, acetoguanamine, ammeline, 2-chloro-4,6-diamino-1,3,5-triazine, 6-methyl-2,4-diamino-1,3,5-triazine, 3,5-diaminotriazole, triaminopyrimidine, 2-mercapto-4,6-diaminopyrimidine, 2,4,6-triethyltriamino-1,3,5-triazine and the like.
  • aldehyde employed is most often formaldehyde
  • other similar condensation products can be made from other aldehydes, such as acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural, and others.
  • the aminoplast resins contain methylol or similar alkylol groups, and it is preferred that at least a portion, most preferably at least 80 percent, of these alkylol groups are etherified by reaction with an alcohol to provide organic solvent-soluble resins.
  • Any monohydric alcohol can be employed for this purpose, including such alcohols as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol and others as well as benzyl alcohol and other aromatic alcohols, cyclic alcohols such as cyclohexanol, monoethers of glycols such as Cellosolves and Carbitols, and halogen-substituted or other substituted alcohols such as 3-chloropropanol.
  • the preferred aminoplast resins are substantially etherified with methanol or butanol, preferably methanol, including, for example, hexamethoxymethylmelamine.
  • alkyl etherified aminoplasts it is especially preferred to employ those which are essentially monomeric compounds (i.e., essentially free of low molecular weight dimers, trimers, etc.) examples of which include those available from American Cyanamid Company as CYMEL 300 and CYMEL 1130.
  • the aminoplasts (sometimes referred to as amine-aldehyde condensation products) are produced in the art using acidic or basic catalysts and varying conditions of time and temperature.
  • the aldehyde is often employed as a solution in water or alcohol, and the condensation and etherification reactions may be carried out either sequentially or simultaneously.
  • hydroxyl-containing carboxylic acids can be employed to prepare the ungelled, thermosetting resins of the invention, including such compounds as glycolic acid, beta-hydroxy propionic acid, alpha-hydroxy butyric acid, dimethylol propionic acid, mandelic acid, 2-hydroxy-3-methylbenzoic acid, 2,4,6-trihydroxybenzoic acid, ricinoleic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, lactic acid, and other aliphatic and aromatic hydroxyl-containing carboxylic acids.
  • Dimethylolpropionic acid, glycolic acid and lactic acid are preferred, and dimethylolpropionic acid is especially preferred.
  • alkylenimines including substituted alkylenimines, can be used to prepare the ungelled, thermosetting reaction products of the invention.
  • the alkylenimines used should have either two or three carbon atoms in the alkylenimine ring or rings.
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen; alkyl or hydroxyalkyl such as methyl, ethyl, propyl, hydroxyethyl, or the like, having for example, up to about 20 carbon atoms; aryl, such as phenyl or the like; alkaryl, such as tolyl, xylyl, or the like; or aralkyl, such as benzyl, phenethyl, or the like.
  • R 6 in the above formula is hydrogen or a lower alkyl radical usually having not more than about 6 carbon atoms; and n is an integer from 0 to 1.
  • the groups designated by the above formula include any substituted radicals of the classes indicated where the substituent groups do not adversely affect the basic nature of the imine in the reaction.
  • substituents can include the groups such as carbonyl, cyano, halo, amino, hydroxy, alkoxy, carbalkoxy and nitrile.
  • the substituted groups may thus be cyanoalkyl, acyl (e.g., acetyl), haloalkyl, aminoalkyl, hydroxyalkyl, alkoxyalkyl, carbalkoxyalkyl, and similar substituted derivatives of aryl, alkaryl, and aralkyl groups where present.
  • alkylenimines within the class described are as follows:
  • the preferred imines are alkylenimines and substituted alkylenimines having 2 to 4 carbon atoms, and especially ethylenimine, 1,2-propylenimine, and N-hydroxyethyl ethylenimine.
  • imines not within the formula indicated may also be used.
  • satisfactory results may be attained by using alkylenimines containing more than one alkylenimine ring such as ethylene-1,2-bisaziridine and 1,2,4-tris(2-1-aziridinylethyl)trimellitate.
  • alkylenimines such as N-aminoethylenimine and the like, can be used. It is to be understood that the term, alkylenimines, as that term is used in the instant invention includes all the above-described alkylenimines, both substituted and otherwise.
  • the ungelled thermosetting resins of the invention can be prepared employing polyols, especially diols, to make the reaction product and incorporation of such polyols is preferred.
  • polyols include, but are not limited to, simple diols and higher hydric alcohols, polyester polyols, and polyether polyols.
  • Examples of the simple diols and higher hydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 2-methyl-1, 3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethylol, 1,2-bis(hydroxymethyl)cyclohexane, 1,2-bis(hydroxyethyl)cyclohexane, trimethylolpropane, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, diethylene glycol, trimethylene glycol,
  • Polyester polyols which may be employed in the preparation of the ungelled thermosetting resins of the invention include the generally known polyester polyols prepared by conventional techniques utilizing simple diols and higher hydric alcohols known in the art (optionally in combination with monohydric alcohols) with polycarboxylic acids. Examples of the simple diols and higher hydric alcohols include those described previously herein.
  • Additional examples include the alkoxylation product of one mole of 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol-A) and 2 moles of propylene oxide available as DOW-565 from Dow Chemical Company, and the like; the polyether glycols such as poly(oxypropylene)glycol and poly(oxytetramethylene)glycol; pentaerythritol; caprolactone triol (e.g. the reaction product of caprolactone and trimethylolpropane) and the like.
  • polycarboxylic acids examples include: phthalic acid; isophthalic acid; terephthalic acid; trimellitic acid; adipic acid; azelaic acid; sebacic acid; succinic acid; malic acid; glutaric acid; malonic acid; pimelic acid; suberic acid; 2,2-dimethylsuccinic acid; 3,3-dimethylglutaric acid; 2,2-dimethylglutaric acid; maleic acid; fumaric acid; itaconic acid; and the like.
  • Anhydrides of the above acids, where they exist, can also be employed and are encompassed by the term "polycarboxylic acid.”
  • certain compounds which react in a manner similar to acids to form polyester polyols are also useful.
  • Such materials include lactones such as caprolactone, propylolactone, and methyl caprolactone, and hydroxy acids such as hydroxy caproic acid and dimethylolpropionic acid. If a triol or other higher hydric alcohol is used, a monocarboxylic acid, such as acetic acid and benzoic acid, may be used in the preparation of the polyester polyol.
  • the polyester polyols include polyester polyols modified with fatty acids or glyceride oils of fatty acids (i.e., conventional alkyd polyols containing such modification).
  • polyester polyols may be prepared by reacting an alkylene oxide such as ethylene oxide, propylene oxide, butylglycidyl ether, and the glycidyl ethers of organic acids such as CARDURA-E, with the carboxylic acid to form the corresponding ester.
  • alkylene oxide such as ethylene oxide, propylene oxide, butylglycidyl ether, and the glycidyl ethers of organic acids such as CARDURA-E
  • polyester polyols examples include: ethanol; propanol; isopropanol; n-pentanol; neopentyl alcohol; 2-ethoxyethanol; 2-methoxyethanol; 1-hexanol; cyclohexanol; 2-methyl-2-hexanol; 2-ethylhexyl alcohol; 1-octanol; 1-nonanol; isodecyl alcohol; and the like.
  • polyether polyols which may be employed to prepare the ungelled thermosetting resins of the invention include the generally known polyether polyols prepared by well known techniques.
  • polyether polyols include the poly(oxyalkylene)glycols prepared by the acid or base catalyzed addition of an alkylene oxide such as ethylene oxide and/or propylene oxide to initiator compounds such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose and the like.
  • polyether polyols include the generally known poly(oxytetramethylene)glycols prepared by the polymerization of tetrahydrofuran in the presence of Lewis acid catalysts such as boron trifluoride, tin (IV) chloride, antimony pentachloride, antimony trichloride, phosphorous pentafluoride, and sulfonyl chloride.
  • Lewis acid catalysts such as boron trifluoride, tin (IV) chloride, antimony pentachloride, antimony trichloride, phosphorous pentafluoride, and sulfonyl chloride.
  • Other examples of polyether polyols include the generally known reaction products of 1,2-epoxide-containing compounds with polyols such as those included in the description of simple diols and higher hydric alcohols above.
  • Preparation of the ungelled, thermosetting reaction products may be carried out by reacting the aminoplast, hydroxyl-containing carboxylic acid, optional polyol, and alkylenimine together in a single step. However it is preferred to first react the aminoplast, hydroxyl-containing carboxylic acid and optional polyol together with removal of the resulting lower alcohol by distillation to form a prereaction product containing carboxyl groups followed by imination of the prereaction product to form an ungelled thermosetting resin of the invention.
  • the aminoplast, hydroxyl-containing carboxylic acid and optional polyol generally are mixed together and reacted by heating to a temperature of up to about 200° C., typically up to about 120° C. while removing the lower alcohol product by distillation.
  • reaction products of the invention for use as grinding resins are prepared by allowing the reaction to proceed until a Gardner-Holdt viscosity of about U to V is obtained for the reaction product at a total theoretical solids content in methylisobutyl ketone of at least about 80 percent by weight.
  • the preferred reaction products for use as grinding resins, prior to imination have an acid value at 100 percent theoretical solids of less than about 13.
  • the preferred reaction products for use as grinding resins have an acid value of less than about 9 at a theoretical total solids content in isobutanol of 80 percent by weight.
  • the acid value of the resulting iminated reaction products may vary widely.
  • the reaction products of the invention have acid values at about 80 percent by weight total solids in isobutanol ranging up to about 80, preferably up to about 50, and more preferably up to about 30.
  • the proportions of aminoplast, hydroxyl-containing carboxylic acid, and optional polyol in the ungelled thermosetting resins of the invention can be varied widely.
  • the resins of the invention are prepared from about 98 to about 50 percent by weight of aminoplast, from about 2 to about 20 percent by weight of hydroxyl-containing carboxylic acid, and from 0 to about 12 percent by weight of polyol based on the total weight of the aforesaid three components.
  • advantages of the invention are achieved when all or part of the acidic groups present are reacted with the alkylenimine, the extent of the modification being dependent upon the amount of imine employed.
  • the ratio of weight of imine to the weight of resin can vary from about 0.1 to about 5 percent, preferably from about 0.5 to about 2.0 percent.
  • the reaction with the alkylenimine can be performed by admixing the imine with the other components for preparing a resin of the invention and heating to a moderate temperature, for example from about 25° C. to about 150° C., although higher or lower temperature may be used depending upon the desired reaction time.
  • a moderate temperature for example from about 25° C. to about 150° C., although higher or lower temperature may be used depending upon the desired reaction time.
  • the aminoplast, hydroxyl-containing carboxylic acid and optional polyol are first reacted together by heating to a temperature of about 80° C. to about 150° C. to form a prereaction product. Thereafter, the alkylenimine is admixed with the prereaction product and the resultant composition is heated to a temperature of about 40° C. to about 100° C.
  • the imine reacts with the acidic groups, but the exact nature of the reaction which takes place under these circumstances and the structure of the product obtained is not known with certainty.
  • thermosetting resins of the invention may themselves be utilized as coating compositions, it is preferred that they be combined with additional components such as other film-forming thermosetting and/or thermoplastic resins, most preferably with other thermosetting resins.
  • additional film-forming thermosetting and/or thermoplastic resins include the generally known cellulosics, acrylics, aminoplasts, urethanes, polyesters, polyethers, polyamides, epoxies or mixtures thereof.
  • the thermosetting resins of the invention and the optional, additional film-forming resins can be employed optionally in combination with various ingredients generally known for use in coating compositions.
  • these various ingredients include: fillers; plasticizers; antioxidants; mildewcides and fungicides; surfactants; various flow control agents including, for example, thixotropes and also additives for sag resistance and/or pigment orientation based on polymer microparticles (sometimes referred to as microgels) described for example in U.S. Pat. Nos. 4,025,474; 4,055,607; 4,075,141; 4,115,472; 4,147,688; 4,180,489; 4,242,384; 4,268,547; 4,220,679; and 4,290,932.
  • Acrylic resins refer to the generally known addition polymers and copolymers of acrylic and methacrylic acids and their ester derivatives, acrylamide and methacrylamide, and acrylonitrile and methacrylonitrile. Additional examples of acrylic monomers which can be addition polymerized to form acrylic resins which may be used in compositions of the invention include methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, stearyl
  • Aminoplast resins refer to the generally known condensation products of an aldehyde with an amino- or amido-group containing substance examples of which include the reaction products of formaldehyde, acetaldehyde, crotonaldehyde, benzaldehyde and mixtures thereof with urea, melamine, or benzoguanimine.
  • Preferred aminoplast resins include the etherified products obtained from the reaction of alcohols and formaldehyde with urea, melamine, or benzoguanimine.
  • suitable alcohols for preparing these etherified products include: methanol, ethanol, propanol, butanol, hexanol, benzylalcohol, cyclohexanol, 3-chloropropanol, and ethoxyethanol.
  • suitable alcohols for preparing these etherified products include: methanol, ethanol, propanol, butanol, hexanol, benzylalcohol, cyclohexanol, 3-chloropropanol, and ethoxyethanol.
  • Additional examples of aminoplast resins include those described previously herein as examples of aminoplasts for preparing resins of the present invention.
  • Urethane resins refer to the generally known thermosetting or thermoplastic urethane resins prepared from organic polyisocyanates and organic compounds containing active hydrogen atoms as found for example in hydroxyl, and amino moieties.
  • Some examples of urethane resins typically utilized in one-pack coating compositions include: the isocyanate-modified alkyd resins sometimes referred to as "uralkyds"; the isocyanate-modified drying oils commonly referred to as "urethane oils” which cure with a drier in the presence of oxygen in air; and isocyanate-terminated prepolymers typically prepared from an excess of one or more organic polyisocyanates and one or more polyols including, for example, simple diols, triols and higher alcohols, polyester polyols and polyether polyols.
  • Polyester resins are generally known and are prepared by conventional techniques utilizing polyhydric alcohols and polycarboxylic acids.
  • suitable polyhydric alcohols include: ethylene glycol; propylene glycol; diethylene glycol; dipropylene glycol; butylene glycol; glycerol; trimethylolpropane; pentaerythritol; sorbitol; 1,6-hexanediol; 1,4-cyclohexanediol; 1,4-cyclohexanedimethanol; 1,2-bis(hydroxyethyl)cyclohexane; and 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate.
  • polycarboxylic acids examples include: phthalic acid; isophthalic acid; terephthalic acid; trimellitic acid; tetrahydrophthalic acid; hexahydrophthalic acid; tetrachlorophthalic acid; adipic acid; azelaic acid; sebacic acid; succinic acid; maleic acid; glutaric acid; malonic acid; pimelic acid; suberic acid; 2-2-dimethylsuccinic acid; 3,3-dimethylglutaric acid; 2,2-dimethylglutaric acid; maleic acid; fumaric acid; and itaconic acid.
  • Anhydrides of the above acids, where they exist, can also be employed and are encompassed by the term "polycarboxylic acid.”
  • certain substances which react in a manner similar to acids to form polyesters are also useful.
  • Such substances include lactones such as caprolactone, propylolactone and methyl caprolactone, and hydroxy acids such as hydroxy caproic acid and dimethylol propionic acid.
  • a triol or higher hydric alcohol is used, a monocarboxylic acid, such as acetic acid and benzoic acid may be used in the preparation of the polyester resin.
  • polyesters which may be used in compositions of the invention are intended to include polyesters modified with fatty acids or glyceride oils of fatty acids (i.e., conventional alkyd resins).
  • Alkyd resins typically are produced by reacting the polyhydric alcohols, polycarboxylic acids, and fatty acids derived from drying, semi-drying, and non-drying oils in various proportions in the presence of a catalyst such as litharge, sulfuric acid, or a sulfonic acid to effect esterification.
  • Suitable fatty acids include saturated and unsaturated acids such as stearic acid, oleic acid, ricinoleic acid, palmitic acid, linoleic acid, linolenic acid, licanic acid, eleostearic acid, and clupanodonic acid.
  • Epoxy resins are generally known and refer to compounds or mixtures of compounds containing more than one 1,2-epoxy group of the formula ##STR2## i.e., polyepoxides.
  • the polyepoxides may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic.
  • suitable polyepoxides include the generally known polyglycidyl ethers of polyphenols and/or polyepoxides which are acrylic resins containing pendant and/or terminal 1,2-epoxy groups.
  • Polyglycidyl ethers of polyphenols may be prepared, for example, by etherification of a polyphenol with epichlorohydrin or dichlorohydrin in the presence of an alkali.
  • suitable polyphenols include: 1,1-bis(4-hydroxyphenyl)ethane; 2,2-bis(4-hydroxyphenyl)propane; 1,1-bis-(4-hydroxyphenyl)isobutane; 2,2-bis(4-hydroxytertiarybutylphenyl)propane; bis(2-hydroxynaphthyl)methane; 1,5-dihydroxynaphthalene; 1,1-bis(4-hydroxy-3-allylphenyl)ethane; and the hydrogenated derivatives thereof.
  • the polyglycidyl ethers of polyphenols of various molecular weights may be produced, for example, by varying the mole ratio of epichlorohydrin to polyphenol in known manner.
  • Epoxy resins also include the polyglycidyl ethers of mononuclear polyhydric phenols such as the polyglycidyl ethers of resorcinol, pyrogallol, hydroquinone, and pyrocatechol.
  • Epoxy resins additionally include polyglycidyl esters of polycarboxylic acids such as the generally known polyglycidyl esters of adipic acid, phthalic acid, and the like.
  • Addition polymerized resins containing epoxy groups may also be employed. These polyepoxides may be produced by the addition polymerization of epoxy functional monomers such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether optionally in combination with ethylenically unsaturated monomers such as styrene, alpha-methyl styrene, alpha-ethyl styrene, vinyl toluene, t-butyl styrene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, ethacrylonitrile, ethyl methacrylate, methyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, and isobornyl methacrylate.
  • epoxy functional monomers such as glycidyl acrylate, glycidyl methacrylate and allyl g
  • the ungelled, thermosetting resins of the invention provide a number of advantages in pigmented coating compositions and are especially suitable as pigment dispersing resins.
  • Pigments suitable for coating compositions containing ungelled, thermosetting resins of the invention include a wide variety of pigments known for use in coating compositions. Suitable pigments include both metallic-flake pigments and various white and colored pigments.
  • Coating compositions utilizing the ungelled, thermosetting resins of the invention may be applied to a wide variety of substrates such as wood, metals, glass, cloth, plastics, foams and the like.
  • the coating compositions can be applied to the substrate utilizing any known application technique including, for example, spraying, brushing, roll coating, doctor blade coating, curtain coating, and the like.
  • Coating compositions containing ungelled, thermosetting resins of the invention typically are cured by heating at temperatures ranging from about 80° C. to about 175° C. Curing times for coating compositions based on thermosetting resins may be subject to wide variation but typically are in the range of from about 10 minutes to about 45 minutes.
  • a reaction vessel equipped with a mechanical stirrer, heating mantle, addition funnel, pot thermometer, and distillation take-off head containing a thermometer, and a condenser is charged with 14581.0 grams (g) of hexamethoxymethyl melamine (available as CYMEL-300 from American Cyanamid Company), 1532.0 g of 1,6-hexanediol, and 765.0 g of dimethylolpropionic acid (DMPA).
  • DMPA dimethylolpropionic acid
  • the resulting reaction product is a resin of the invention.
  • the reaction product has an acid value of 6.0, a Gardner-Holdt viscosity of X-Y, a total solids content measured for 2 hours at 105° C. of 77.4 percent by weight, a total solids content measured for 2 hours at 150° C. of 64.3 percent by weight, a color value of 1-2, a hydroxyl number of 25.8, and a free HEEI content of 28 parts per million by weight.
  • a resin of the invention is prepared from 85.71 parts by weight (pbw) of CYMEL-300, 9.00 pbw of 1,6-hexanediol, 4.50 pbw of DMPA, 0.79 pbw of HEEI, and about 23.3 pbw of isobutanol according to a procedure similar to that described in EXAMPLE 1.
  • the resulting reaction product has an acid value of 6.2 and a hydroxyl value of 27.0.
  • a sample of the resulting pigment dispersion is drawn down on a glass panel by means of a 3 mil drawdown bar to produce a wet film of the pigment dispersion on the glass panel.
  • the wet film is visually examined by looking through the film into a lighted background and examined for "color development” and "transparency".
  • the wet film exhibits excellent color development in that the film is of a uniform, rich red color.
  • the wet film exhibits excellent transparency, meaning that printed matter can be read easily as viewed through the wet film on the glass plate.

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  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US06/594,185 1984-03-28 1984-03-28 Curable, iminated resins from aminoplasts and hydroxyl-containing carboxylic acids Expired - Fee Related US4528333A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US06/594,185 US4528333A (en) 1984-03-28 1984-03-28 Curable, iminated resins from aminoplasts and hydroxyl-containing carboxylic acids
CA000476757A CA1242839A (en) 1984-03-28 1985-03-18 Curable, iminated resins from aminoplasts and hydroxyl-containing carboxylic acids
DE8585103472T DE3563213D1 (en) 1984-03-28 1985-03-25 Curable iminated resins from aminoplasts and hydroxylcontaining carboxylic acids
EP85103472A EP0158874B1 (en) 1984-03-28 1985-03-25 Curable iminated resins from aminoplasts and hydroxylcontaining carboxylic acids
ES541571A ES8607360A1 (es) 1984-03-28 1985-03-26 Un metodo para preparar una resina sintetica no gelificada.
JP60066426A JPS60228524A (ja) 1984-03-28 1985-03-28 非ゲル化合成樹脂を含む被覆組成物

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US06/594,185 US4528333A (en) 1984-03-28 1984-03-28 Curable, iminated resins from aminoplasts and hydroxyl-containing carboxylic acids

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US (1) US4528333A (enrdf_load_stackoverflow)
EP (1) EP0158874B1 (enrdf_load_stackoverflow)
JP (1) JPS60228524A (enrdf_load_stackoverflow)
CA (1) CA1242839A (enrdf_load_stackoverflow)
DE (1) DE3563213D1 (enrdf_load_stackoverflow)
ES (1) ES8607360A1 (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4775597A (en) * 1987-06-15 1988-10-04 Ppg Industries, Inc. Ultraviolet light curable compositions for application to porous substrates based on unsaturated polyesters reacted with amino alcohols
US4788108A (en) * 1987-06-15 1988-11-29 Ppg Industries, Inc. Ultraviolet light curable compositions based on iminated unsaturated polyesters for application to porous substrates
US5965670A (en) * 1997-12-24 1999-10-12 Ppg Industries Ohio, Inc. Curable-film forming compositions having improved mar and acid etch resistance
US20100221559A1 (en) * 2007-10-03 2010-09-02 Kaoru Konno Adhesive composition, electronic-component-mounted substrate and semiconductor device using the adhesive composition
US9023326B2 (en) 2009-07-21 2015-05-05 Nail Alliance Llc Compositions for removable gel applications for nails and methods of their use

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US3290417A (en) * 1965-06-01 1966-12-06 Pittsburgh Plate Glass Co Thermosetting coating compositions modified with an alkylenimine
US3502557A (en) * 1965-04-01 1970-03-24 Ppg Industries Inc Electrodeposition of amine-aldehyde condensate and hydroxy-containing carboxylic acid coreaction products
US3519627A (en) * 1968-04-09 1970-07-07 Ashland Oil Inc Carboxyl-containing ethers of amino-triazine/aldehyde condensates
US3917570A (en) * 1973-05-16 1975-11-04 Ppg Industries Inc Polyurethane polyester-polyol compositions modified with an alkylenimine
US3965058A (en) * 1965-04-01 1976-06-22 Ppg Industries, Inc. Coreaction products
US4026855A (en) * 1974-11-19 1977-05-31 American Cyanamid Company Composition of matter particularly adaptable for use in electrodepositing films on metal
US4403091A (en) * 1982-09-28 1983-09-06 Ppg Industries, Inc. Ungelled hydroxy group-containing oligomers

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CA553155A (en) * 1951-08-31 1958-02-11 Ciba Limited Salts of new hardenable, basic, ternary condensation products derived from methylol compounds of aminotriazines or of urea
GB1102384A (en) * 1965-10-11 1968-02-07 Coates Brothers & Co Melamine-formaldehyde resins for electrodeposition

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US3290416A (en) * 1964-06-22 1966-12-06 Pittsburgh Plate Glass Co Methacrylate polymer coating composition modified with an alkylenimine
US3502557A (en) * 1965-04-01 1970-03-24 Ppg Industries Inc Electrodeposition of amine-aldehyde condensate and hydroxy-containing carboxylic acid coreaction products
US3965058A (en) * 1965-04-01 1976-06-22 Ppg Industries, Inc. Coreaction products
US3290417A (en) * 1965-06-01 1966-12-06 Pittsburgh Plate Glass Co Thermosetting coating compositions modified with an alkylenimine
US3519627A (en) * 1968-04-09 1970-07-07 Ashland Oil Inc Carboxyl-containing ethers of amino-triazine/aldehyde condensates
US3917570A (en) * 1973-05-16 1975-11-04 Ppg Industries Inc Polyurethane polyester-polyol compositions modified with an alkylenimine
US4026855A (en) * 1974-11-19 1977-05-31 American Cyanamid Company Composition of matter particularly adaptable for use in electrodepositing films on metal
US4403091A (en) * 1982-09-28 1983-09-06 Ppg Industries, Inc. Ungelled hydroxy group-containing oligomers

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4775597A (en) * 1987-06-15 1988-10-04 Ppg Industries, Inc. Ultraviolet light curable compositions for application to porous substrates based on unsaturated polyesters reacted with amino alcohols
US4788108A (en) * 1987-06-15 1988-11-29 Ppg Industries, Inc. Ultraviolet light curable compositions based on iminated unsaturated polyesters for application to porous substrates
US5965670A (en) * 1997-12-24 1999-10-12 Ppg Industries Ohio, Inc. Curable-film forming compositions having improved mar and acid etch resistance
US20100221559A1 (en) * 2007-10-03 2010-09-02 Kaoru Konno Adhesive composition, electronic-component-mounted substrate and semiconductor device using the adhesive composition
US9247652B2 (en) * 2007-10-03 2016-01-26 Hitachi Chemical Company, Ltd. Adhesive composition, electronic-component-mounted substrate and semiconductor device using the adhesive composition
US10504864B2 (en) 2007-10-03 2019-12-10 Hitachi Chemical Company, Ltd. Adhesive composition, electronic-component-mounted substrate and semiconductor device using the adhesive composition
US9023326B2 (en) 2009-07-21 2015-05-05 Nail Alliance Llc Compositions for removable gel applications for nails and methods of their use
US9084738B2 (en) 2009-07-21 2015-07-21 Nail Alliance Llc Compositions for removable gel applications for nails and methods of their use
US9084737B2 (en) 2009-07-21 2015-07-21 Nail Alliance Llc Compositions for removable gel applications for nails and methods of their use
US9526686B2 (en) 2009-07-21 2016-12-27 Nail Alliance, Llc Compositions for removable gel applications for nails and methods of their use

Also Published As

Publication number Publication date
DE3563213D1 (en) 1988-07-14
ES8607360A1 (es) 1986-05-16
JPS60228524A (ja) 1985-11-13
ES541571A0 (es) 1986-05-16
EP0158874A2 (en) 1985-10-23
JPS6353232B2 (enrdf_load_stackoverflow) 1988-10-21
CA1242839A (en) 1988-10-04
EP0158874A3 (en) 1986-07-16
EP0158874B1 (en) 1988-06-08

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